Carbon-coated metal powder, conductive paste containing carbon-coated metal powder and multilayer electronic component using same, and method for manufacturing carbon-coated metal powder

ABSTRACT

This invention aims at providing a carbon-coated metal powder having few impurities, a narrower particle size distribution, and sintering properties particularly suitable as a conductive powder of a conductive paste for forming internal conductors in a ceramic multilayer electronic component obtained by co-firing multilayered ceramic sheets and internal conductor layers; a conductive paste containing the carbon-coated metal powder; a multilayer electronic component using the conductive paste; and a method for manufacturing the carbon-coated metal powder. The carbon-coated metal powder has specific properties in TMA or ESCA measurements. The carbon-coated metal powder can be obtained by melting and vaporizing a metallic raw material in a reaction vessel, conveying the generated metal vapor into a cooling tube and rapidly cooling the metal vapor by endothermically decomposing a carbon source supplied into the cooling tube, and forming a carbon coating film on metal nuclei surfaces in parallel with generation of the metal nuclei.

TECHNICAL FIELD

The present invention relates to a carbon-coated metal powder, which isparticularly advantageous for forming for example, internal conductors(internal electrodes), terminal electrodes, etc. of multilayerelectronic components, a conductive paste containing the carbon-coatedmetal powder, and a multilayer electronic component using the same.

The present invention also relates to a method for manufacturing acarbon-coated metal powder, and more particularly to a method formelting and vaporizing a metal material, rapidly cooling the metal vaporby endothermic decomposition of a supplied carbon source, and forming acarbon coating film on the surfaces of metal nuclei in parallel withgeneration of the metal nuclei.

BACKGROUND ART

Ceramic multilayer electronic components, such as multilayer capacitorsand multilayer inductors, and ceramic multilayer substrates aregenerally manufactured by alternately laminating a plurality of unfiredceramic green sheets of dielectric, magnetic materials or the like andinternal conductive paste layers, and co-firing the laminate at a hightemperature. Noble metals have been mainly used for the internalconductors, but base metal materials such as nickel, etc. have recentlyfound wide application.

When nickel particles are fired in a non-oxidizing atmosphere such as aninert atmosphere or reducing atmosphere to prevent oxidation, sinteringoccurs at an early stage, and sintering and shrinkage start at a lowtemperature of 400° C. or less even when single-crystal particles with acomparatively low activity are used. Meanwhile, sintering of ceramiclayers generally starts at a much higher temperature than the abovetemperature. For example, barium titanate starts sintering at about1200° C. A problem occurring because of such a difference in shrinkagebehavior is that when an internal conductive paste containing a nickelpowder and ceramic sheets are co-fired, the ceramic layers do not shrinktogether with the nickel films, and therefore delamination or cracks caneasily occur between the internal conductor layers and ceramic layers.

With one of the suggested methods for solving the aforementionedproblem, the sintering initiation temperature of nickel particles isincreased, for example, by coating carbon on the nickel particles orincorporating carbon therein (PTL (patent literature) 1 and PTL 2). PTL1 discloses a metal powder in which a carbon coating film is formed onnickel powder surface by producing a nickel powder by a vapor phasehydrogen-reduction method, or the like, and then bringing the nickelpowder into contact with a hydrocarbon gas at 300° C. to 600° C. PTL 2discloses a carbon-containing nickel particle powder obtained by heatinga dispersion liquid containing nickel particles and a polyol at 150° C.to 350° C. to cause carbon adsorption on the surfaces of nickelparticles and/or permeation of carbon into the nickel particles.

Further, surface modification by coating a carbon film on fine metalparticles of nickel, or the like, which are used in sensors or magneticmaterials, this application being entirely different from that describedhereinabove, is also known. For example, PTL 3 and PTL 4 discloseproducing nickel particles coated with carbon by cooling a metal vapor,which is generated by melting and vaporizing a metallic raw material,under an atmosphere including a hydrocarbon gas such as methane gas.

CITATION LIST Patent Literature

PTL 1: Japanese Patent Application Publication No. 2005-008960.

PTL 2: Japanese Patent Application Publication No. 2005-154904.

PTL 3: Japanese Patent Application Publication No. 563-020032.

PTL 4: Japanese Patent Application Publication No. 2010-212580.

PTL 5: Japanese Patent Application Publication No. 2014-029012.

PTL 6: Japanese Patent Application Publication No. 2014-029013.

SUMMARY OF INVENTION Technical Problem

However, the following problems are associated with the above-describedconventional techniques.

With the manufacturing methods disclosed in PTL 1 and PTL 2, a nickelpowder is generated in advance, and a carbon film is coated on thegenerated nickel powder or carbon is introduced therein. Therefore, anoxide film is most often formed on the nickel powder surface beforecarbon is coated or introduced. Once the oxide film is formed on thesurface, the film is difficult to remove completely. In particular, inthe case of nickel particles of a small size, the surface activity isvery high, and therefore the oxide film is even more difficult toremove. Further, the removal of natural oxide film from thecarbon-coated nickel powder obtained with the method disclosed in PTL 1leaves depressions there.

Where an oxide film is present on the nickel powder surface, a nickelpowder is produced in which the carbon coating film is formed on theoxide film. When a conductive paste is produced using such acarbon-coated nickel powder and the paste is fired, oxygen of the oxidefilm reacts with carbon of the carbon coating film during firing and isreleased as carbon dioxide. Therefore, a good fired film which is dense,free of defects, and excellent in continuity cannot be obtained.Further, in the methods disclosed in PTL 1 and PTL 2, since the carboncoating film is formed by heat treatment at a temperature lower than thedecomposition temperature of the hydrocarbon compound producing thecarbon film, the carbon coating film is formed that includes a largeamount of impurities such as hydrogen and oxygen. Since the carboncoating film includes such impurities, gas is generated during firingand a good fired film cannot be obtained as in the above case. Anotherproblem is that since impurities are included in the carbon coating filmand nickel particles themselves, sufficient electric conductivity cannotbe obtained.

The investigation conducted by the inventors revealed that the nickelparticles obtained by the methods disclosed in PTL 3 and PTL 4 have avery broad particle size distribution and nickel particles with a narrowparticle size distribution, which are required for the aforementionedinternal conductor, cannot be obtained. This is supposedly because themetal vapor produced by melting and vaporization of a metallic rawmaterial is difficult to cool uniformly and nickel nuclei are generatedat different timings.

Further, the carbon-containing nickel powder disclosed in PTL 2 wasproposed to improve a shrinkage characteristic, and although theshrinkage start temperature can be as high as 931° C. or 1007° C., sincethe shrinkage starts abruptly when the shrinkage start temperature isreached, the problem associated with the likelihood of occurrence ofdelamination or cracking between the ceramic layer and internalconductor layer during firing performed at a high temperature of 1200°C. or higher cannot be fully resolved.

PTL 5 and PTL 6 likewise disclose the inventions aimed to improve theshrinkage characteristic of nickel powder. In the inventions disclosedin PTL 5 and PTL 6, the shrinkage characteristic of nickel powder isimproved by coating nickel powder with nickel oxide or nickel hydroxide,rather than coating nickel powder with carbon. However, in theinventions disclosed in PTL 5 and PTL 6, the shrinkage behavior at a lowtemperature equal to or lower than 400° C. is particularly considered,and the shrinkage behavior up to a temperature as high as 1200° C. isnot considered. Therefore, the problem that delamination or cracks areeasily generated is not sufficiently resolved, in the same manner asdescribed hereinabove.

Further, in PTL 5 and PTL 6, nickel oxide or nickel hydroxide is presentand the state of the coating film, or the like, on the surfaces ofnickel particles is not analyzed in detail by X-ray photoelectronspectroscopy (XPS, ESCA). Therefore, the improvement of shrinkagecharacteristic is not sufficient and the problem that delamination orcracks are easily generated is not sufficiently resolved, in the samemanner as described hereinabove.

The present invention has been made to solve the abovementionedproblems, and it is an objective of the present invention to provide acarbon-coated metal powder with few impurities and a narrow particlesize distribution, the carbon-coated metal powder enabling the formationof multilayer electronic components with few defects, such asdelamination and cracks, when used for a conductive paste for forminginternal conductors and electrodes of multilayer electronic components.It is another objective of the present invention to provide a conductivepaste containing the carbon-coated metal powder and a multilayerelectronic component using the conductive paste.

Yet another objective of the present invention is to provide a methodfor manufacturing a carbon-coated metal powder with few impurities and anarrow particle size distribution.

Solution to Problem

The carbon-coated metal powder in accordance with the present inventioncomprises a metal powder and a carbon coating film that covers the metalpowder, wherein

when 10% value, 50% value, and 90% value in a volume-based cumulativefraction in the particle size distribution measurements by a laserdiffraction method are denoted by D10, D50, and D90, respectively, D50is 300 nm or less, and an SD value represented by (D90−D10)/(D50) is 1.5or less;

an oxygen content in a weight proportion of an oxygen component to thecarbon-coated metal powder of a unit weight is 1500 ppm or less perspecific surface area of 1 m²/g of the powder; and

X represented by Expression (1) is 50 or less when a TMA(thermomechanical analysis) measurement is performed by raising atemperature from a room temperature to 1200° C. at a rate of 5° C./rainin a nitrogen-hydrogen reducing atmosphere:

X (%)=(X _(200° C.) /X _(MAX))×100

(in Expression (1), X_(MAX) is a maximum shrinkage percentage andX_(200° C.) is a maximum value in differences, each of which is adifference between a maximum shrinkage percentage and a minimumshrinkage percentage in a temperature width of 200° C.)

Further, the carbon-coated metal powder in accordance with the presentinvention comprises a nickel-based powder of nickel or containing nickelas a main component, and a carbon coating film that covers thenickel-based powder, wherein

an oxygen content in a weight proportion of an oxygen component to thecarbon-coated metal powder of a unit weight is 1500 ppm or less perspecific surface area of 1 m²/g of the powder; and

in a surface analysis by ESCA, a peak position attributable to 1 s of acarbon atom in a position at 11 nm from a particle surface toward aparticle center is shifted to a low-energy side with respect to the peakposition in a position at 1 nm from the particle surface toward theparticle center. The above-mentioned shift to the low-energy side in thesurface analysis by ESCA is preferably 0.08 eV or more. It is preferredthat peaks attributable to nickel oxide and nickel hydroxide be notpresent. This carbon-coated metal powder can be also referred to as“carbon-coated nickel-based powder”. It is also preferred that thiscarbon-coated metal powder (carbon-coated nickel-based powder) furtherhas the above-described properties (D50, SD value, X defined by the TMAmeasurements) specified with respect to the carbon-coated metal powdercharacterized by the TMA or the like.

A method for manufacturing a carbon-coated metal powder in accordancewith the present invention includes:

a metal vapor generation step for heating a metallic raw material in areaction vessel and melting and vaporizing the metallic raw material togenerate a metal vapor;

a conveying step for conveying the metal vapor by a carrier gas from thereaction vessel to a cooling tube;

a metal nuclei generation step for cooling the metal vapor inside thecooling tube and generating metal nuclei; and

a metal nuclei growth step for growing the generated metal nuclei,wherein

in the metal nuclei generation step, a carbon source is supplied intothe cooling tube and endothermically decomposed to cool rapidly themetal vapor and cause the formation of a carbon coating film on thesurfaces of the metal nuclei in parallel with the metal nucleigeneration.

The carbon-coated metal powder in accordance with the present inventioncan be obtained by the abovementioned manufacturing method.

Advantageous Effects of Invention

The carbon-coated metal powder in accordance with the present inventionis a fine powder having few impurities and a narrow particle sizedistribution. The powder demonstrates suitable sintering behavior whenused for a conductive paste for forming internal conductors andelectrodes of multilayer electronic components and can form a very thinelectrode with few cavities. Therefore, a multilayer electroniccomponent with few defects such as delamination and cracks can beobtained using the conductive paste.

The carbon-coated metal powder in accordance with the present inventioncan be obtained by the above-described manufacturing method.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram illustrating an example of the structureof a plasma device for use in the method for manufacturing thecarbon-coated metal powder in accordance with the present invention.

FIG. 2 is a schematic diagram illustrating another example of thestructure of a plasma device for use in the method for manufacturing thecarbon-coated metal powder in accordance with the present invention.

FIG. 3 is a TEM (transmission electron microscope) image of thecarbon-coated metal powder obtained in Example 1.

FIG. 4 shows a TMA chart of the carbon-coated metal powders obtained inExamples 1 to 5, 8, and 11.

FIG. 5 shows a TMA chart of the carbon-coated metal powders obtained inComparative Examples 1 and 3 to 5.

FIG. 6 shows the change in intensity of a is peak of carbon with theargon ion etching depth in the results of surface analysis measured byESCA within a binding energy range of 276 eV to 294 eV for thecarbon-coated metal powder obtained in Example 5.

FIG. 7 shows the change in intensity of a is peak of carbon with theargon ion etching depth in the results of surface analysis measured byESCA within a binding energy range of 276 eV to 294 eV for thecarbon-coated metal powder obtained in Example 8.

FIG. 8 shows the change in intensity of a is peak of carbon with theargon ion etching depth in the results of surface analysis measured byESCA within a binding energy range of 276 eV to 294 eV for thecarbon-coated metal powder obtained in Example 11.

FIG. 9 shows the change in intensity of a is peak of carbon with theargon ion etching depth in the results of surface analysis measured byESCA within a binding energy range of 276 eV to 294 eV for thecarbon-coated metal powder obtained in Comparative Example 3.

FIG. 10 shows the results of surface analysis measured by ESCA within abinding energy range of 850 eV to 880 eV for the carbon-coated metalpowder obtained in Example 5.

FIG. 11 shows the results of surface analysis measured by ESCA within abinding energy range of 850 eV to 880 eV for the carbon-coated metalpowder obtained in Example 8.

FIG. 12 shows the results of surface analysis measured by ESCA within abinding energy range of 850 eV to 880 eV for the carbon-coated metalpowder obtained in Example 11.

FIG. 13 is an SEM (scanning electron microscope) image of thecarbon-coated metal powder obtained in Example 1.

FIG. 14 is an SEM image of the carbon-coated metal powder obtained inComparative Example 3.

FIG. 15 is an SEM image of the fired film formed using the carbon-coatedmetal powder obtained in Example 1.

FIG. 16 is an SEM image of the fired film formed using the carbon-coatedmetal powder obtained in Example 1-1.

FIG. 17 is an SEM image of the fired film formed using the carbon-coatedmetal powder obtained in Comparative Example 3.

FIG. 18 is an SEM image of the fired film formed using the carbon-coatedmetal powder obtained in Comparative Example 5.

DESCRIPTION OF EMBODIMENTS

The present invention will be explained hereinbelow on the basis ofspecific embodiments thereof, but the present invention is not limitedthereto. Numerical ranges represented by “ . . . to . . . ” in thedescription include the numerical values standing before and after the“to”.

The carbon-coated metal powder in accordance with the present inventioncomprises a metal powder and a carbon coating film that covers the metalpowder. This powder is particularly advantageous for forming internalconductors (internal electrodes) or terminal electrodes of multilayerelectronic components, but this application is not limiting and thepowder may be also used for other various applications.

[Carbon-Coated Metal Powder]

A metal of the carbon-coated metal powder is not particularly limited,but a base metal is preferred, and a metal containing at least one ofnickel and copper is particularly preferred. Specific examples ofparticularly preferred metal powders include a nickel powder consistingessentially of nickel only, a copper powder consisting essentially ofcopper only, and a powder constituted by nickel and copper. “Consistingessentially of nickel only”, as referred to herein, means that nickel iscontained in an amount of more than 98 wt. % in the metal powder.Likewise, “consisting essentially of copper only”, as referred toherein, means that copper is contained in an amount of more than 98 wt.% in the metal powder. A nickel powder containing copper in an amount of2 wt. % to 20 wt. % is particularly preferred as the metal powderconstituted by nickel and copper.

In the carbon-coated metal powder, where 10% value, 50% value, and 90%value in a volume-based cumulative fraction in particle sizedistribution measurements by laser diffraction method are denoted byD10, D50, and D90, respectively, D50 is 300 nm or less, and an SD valuerepresented by (D90−D10)/(D50) is 1.5 or less. D50 is preferably 100 nmto 300 nm, more preferably 150 nm to 300 nm. It is also desirable thatthe SD value be as small as possible, but in terms of production andcost, a value equal to or less than 0.5 is difficult to obtain.

The thickness of the carbon coating film can be determined from a TEMobservation image, and the preferred thickness is 2 nm to 15 nm. Withinthis range, a sufficient sintering suppression effect can be obtainedand the amount of carbon remaining after firing can be suppressed.

As for the oxygen content in the carbon-coated metal powder, the weightproportion of an oxygen component to the carbon-coated metal powder of aunit weight is 1500 ppm or less, preferably 1000 ppm or less, even morepreferably 800 ppm or less, per specific surface area of 1 m²/g of thepowder, and it is desirable that this oxygen content be as small aspossible, but a value equal to or less than 10 ppm is difficult toobtain. The specific surface area herein is measured by a BET method.For example, “1500 ppm or less per specific surface area of 1 m²/g ofthe powder” means that where the specific surface area of thecarbon-coated metal powder is a m²/g, the oxygen content in thecarbon-coated metal powder of a unit weight is equal to or less than(a×1500) ppm, that is, equal to or less than 1500×10⁻⁶ g per surfacearea of 1 m² of the carbon-coated metal powder.

It is desirable that the content of carbon be 0.5 wt. % to 3.50 wt. %and the content of oxygen be equal to or less than 1 wt. %, and as smallas possible, in the carbon-coated metal powder, the specific contentsbeing different depending on the particle size. It is also preferredthat the content of impurities including oxygen be reduced to 3 wt. % orless. Within the above-described ranges, the amounts of carbon andimpurities remaining after firing can be suppressed.

Further, in the carbon-coated metal powder, X represented by Expression(1) is 50 or less when thermomechanical analysis (TMA) measurements areperformed by raising a temperature from a room temperature to 1200° C.at a rate of 5° C./min in a nitrogen-hydrogen reducing atmosphere.

X (%)=(X _(200° C.) /X _(MAX))×100  (1)

Here, the room temperature is about 25° C. to 30° C. In Expression (1),X_(MAX) is a maximum shrinkage percentage, that is, a maximum shrinkagepercentage within a range from a room temperature to 1200° C.X_(200° C.) is a maximum value in differences, each of which is adifference between a maximum shrinkage percentage and a minimumshrinkage percentage in a temperature width of 200° C., namely, a valuedetermined by obtaining each difference between a maximum shrinkagepercentage and a minimum shrinkage percentage in a temperature width of200° C. over the range of from the room temperature to 1200° C. andtaking the maximum value among the differences. For example, referringto FIGS. 4 and 5, the difference between the maximum shrinkagepercentage and minimum shrinkage percentage in a temperature width of200° C. in which the curve representing the thermal shrinkage percentageversus the rising temperature changes most rapidly is taken asX_(200° C.) Thus, the X (%) calculated from the Expression (1) is anindicator that indicates the degree to which the carbon-coated metalpowder has rapidly shrunk within a range from a room temperature to1200° C. The higher is this value the more rapid is the shrinking.

It is preferred that the X_(MAX) be less than 19.5%. Further, when thetemperature width of 200° C. giving the X_(200° C.) is taken as T to(T+200)° C., it is preferred that T° C.>400° C. Thus, it is preferredthat the start temperature of the temperature width of 200° C. in whichthe difference between the maximum shrinkage percentage and minimumshrinkage percentage reaches a maximum be higher than 400° C. Further,where a maximum shrinkage percentage in a range from a room temperatureto 400° C. is denoted by X′_(MAX), it is preferred that X′ representedby X′ (%)=(X′_(MAX)/X_(MAX))×100 be 30 or less, more preferably 25 orless. As a result, defects which are caused by mismatch in sinteringbehavior are unlikely to occur when the conductor layers formed from theconductive paste containing the carbon-coated metal powder are co-firedwith ceramic sheets.

[Carbon-Coated Metal Powder (Carbon-Coated Nickel-Based Powder)]

Described hereinbelow is a carbon-coated metal powder which has anickel-based powder and a carbon coating film on the nickel-basedpowder, this carbon-coated metal powder having the below-describedproperties determined by surface analysis by ESCA. To facilitate theexplanation herein, the carbon-coated metal power is described as a“carbon-coated nickel-based powder”.

The “nickel-based powder” is a nickel-based powder consistingessentially of nickel only or containing nickel as the main component.“Consisting essentially of nickel only”, as referred to herein, meansthat nickel is contained in an amount of higher than 98 wt. % in themetal powder. Further, “containing nickel as the main component” meansthat nickel is contained in an amount of higher than 50 wt. % in themetal powder. A nickel powder containing copper, in particular, a nickelpowder containing copper in an amount of 2 wt. % to 20 wt. % ispreferred as the nickel-based powder containing nickel as the maincomponent.

In the carbon-coated nickel-based powder, the oxygen content in theweight proportion of an oxygen component to the carbon-coated metalpowder of a unit weight is 1500 ppm or less, preferably 1000 ppm orless, even more preferably 800 ppm or less, per specific surface area of1 m²/g of the powder, and it is desirable that the oxygen content be assmall as possible, but a value equal to or less than 10 ppm is difficultto obtain. The contents of carbon and impurities including oxygen arethe same as in the above-described carbon-coated metal powder.

In the carbon-coated nickel-based powder, the position of a peakattributable to 1 s of a carbon atom changes from the particle surfacetoward the particle center in surface analysis by ESCA. A peak positionattributable to 1 s of a carbon atom in a position at 11 nm from theparticle surface toward the particle center is shifted to a low-energyside with respect to the peak position in a position at 1 nm from theparticle surface toward the particle center. This shift to thelow-energy side is preferably 0.08 eV or more, and a carbon-coatednickel-based powder in which the amount of the shift is 1.00 eV or lessis easy to obtain. The peak attributable to 1 s of a carbon atom isspecifically a peak present in the vicinity of a binding energy of about284.6 eV. The reason for such shifting is considered hereinbelow.

The position at 1 nm from the particle surface toward the particlecenter is in the vicinity of the carbon coating film surface and a largeamount of carbon is present therein. The position at 11 nm from theparticle surface toward the center is in the vicinity of the interfaceof the carbon coating film and the nickel-based powder, and a nickelcarbide layer formed by carbon and nickel is present therein. Thus,electron states differ between the positions at 1 nm and 11 nm from theparticle surface toward the center, and therefore a shift occurs.

As a result of a continuous change from nickel to the carbon layer dueto such a nickel carbide layer, a strong carbon coating film with a highadhesive strength can be formed.

In the carbon-coated nickel-based powder in accordance with the presentinvention, it is preferred that peaks attributable to nickel oxide andnickel hydroxide be not present in the particle surface, as determinedby surface analysis by ESCA. The peak attributable to nickel oxide isspecifically a peak present in the vicinity of a binding energy of about854.0 eV. The peak attributable to nickel hydroxide is specifically apeak present in the vicinity of a binding energy of about 855.7 eV.

Since nickel oxide and nickel hydroxide thus hardly exist in theparticle surface, the content of oxygen in the carbon-coatednickel-based powder in accordance with the present invention can begreatly reduced.

With the carbon-coated nickel-based powder having such features, it ispossible to obtain a carbon-coated nickel-based powder having very fewimpurities. It is also preferred that in addition to the above-describedproperties and features, the carbon-coated nickel-based powder have thesame properties (TMA properties, etc.) as those of the aforementionedcarbon-coated metal powder specified by TMA properties and also theproperties, such as the thickness of the carbon coating film, which aredescribed as being preferred for the aforementioned carbon-coated metalpowder specified by TMA properties. As a result, additional effects canbe obtained.

[Method for Manufacturing Carbon-Coated Metal Powder]

A method for manufacturing a carbon-coated metal powder in accordancewith the present invention includes: a metal vapor generation step forheating a metallic raw material in a reaction vessel and melting andvaporizing the metallic raw material to generate a metal vapor; aconveying step for conveying the metal vapor with a carrier gas from thereaction vessel to a cooling tube; a metal nuclei generation step forcooling the metal vapor inside the cooling tube and generating metalnuclei; and a metal nuclei growth step for growing the generated metalnuclei. In this method in the metal nuclei generation step, a carbonsource is supplied into the cooling tube and endothermically decomposedto cool rapidly the metal vapor and cause the formation of a carboncoating film on the surfaces of the metal nuclei in parallel with themetal nuclei generation. With this manufacturing method, it is possibleto obtain the carbon-coated metal powder in accordance with the presentinvention.

The method for manufacturing a carbon-coated metal powder in accordancewith the present invention will be explained hereinbelow in greaterdetail with reference to the appended drawings.

Initially, a plasma device to be used in the method for manufacturing acarbon-coated metal powder in accordance with the present invention willbe explained with reference to FIG. 1. FIG. 1 is a schematic diagramillustrating an example of the configuration of a plasma device 100 tobe used in the method for manufacturing a carbon-coated metal powder inaccordance with the present invention.

A metallic raw material is accommodated inside a reaction vessel 101. Afeed port 107 serves to supply the metallic raw material into thereaction vessel 101. A predetermined amount of the metallic raw materialis prepared inside the reaction vessel 101 before the operation of thedevice is started, and after the operation of the device has beenstarted, the metallic raw material is supplied from the feed port 107into the reaction vessel 101 as required in accordance with the amountof the metallic raw material discharged as a metal vapor from the insideof the reaction vessel 101. Therefore, the plasma device 100 inaccordance with the present invention is suitable for long-termcontinuous manufacture of the carbon-coated metal powder.

A plasma torch 102 is disposed above the reaction vessel 101, and aplasma generating gas is supplied to the plasma torch 102 through asupply tube (not depicted in the figure). The plasma torch 102 generatesplasma 103 between a cathode 104 and an anode (not depicted in thefigure) which is provided inside the plasma torch 102, and thengenerates plasma 103 between the cathode 104 and an anode 105, at leastpart of the metallic raw material located inside the reaction vessel 101is melted by the heat of the plasma 103, and a metal melt 108 isgenerated. The plasma torch 102 also vaporizes part of the melt 108 withthe heat of the plasma 103, thereby generating a metal vapor.

A carrier gas supply unit 106 supplies a carrier gas, which serves forconveying the metal vapor, into the reaction vessel 101.

A cooling tube 110 is connected to the reaction vessel 101. The metalvapor generated inside the reaction vessel 101 is conveyed by thecarrier gas into the cooling tube 110.

The cooling tube 110 is provided with an indirect cooling zone IC forindirectly cooling the metal vapor and a direct cooling zone DC fordirectly cooling the carbon-coated metal powder, in the order ofdescription from the reaction vessel 101 side (upstream side). Theindirect cooling zone IC is constituted by two tubes, namely, an innertube 112 and an outer tube 113. A cooling fluid is circulated in a spacebetween the outer wall of the inner tube 112 and the inner wall of theouter tube 113, and the periphery of the cooling tube 110 (inner tube112) is cooled or heated. As a result, the temperature of the indirectcooling zone IC is controlled. Further, inside the indirect cooling zoneIC, the indirect cooling is performed with respect to the metal vaporfrom the reaction vessel 101, and also the carbon-coated metal powdergenerated by the formation of a carbon coating film on the metal nucleisurfaces in parallel with the generation of metal nuclei from the metalvapor. The carbon source to be supplied for forming the carbon coatingfilm is described hereinbelow.

The aforementioned carrier gas or other gas can be used as the coolingfluid. Liquids such as water, warm water, methanol, ethanol, or mixturesthereof can also be used. From the standpoint of cooling efficiency andcost, water or warm water is preferably used as the cooling fluid. Usinga cooling fluid is explained herein as an example of the method forcooling or heating the periphery of the cooling tube 110 (inner tube112), but the cooling or heating method is not limited to this. Forexample, an external heater may be provided on the periphery of thecooling tube 110 for cooling or heating.

In the direct cooling zone DC, direct cooling is performed by sprayingor mixing a cooling fluid supplied from a cooling fluid supply unit (notdepicted in the figure) to the carbon-coated metal powder which has beenconveyed from the indirect cooling zone IC. The cooling fluid used inthe direct cooling zone DC may be the same as or different from thecooling fluid used in the indirect cooling zone IC, but from thestandpoint of handleability and cost, it is preferred that gas same asthe above-mentioned carrier gas be used. When the cooling fluid includesa liquid, the liquid is introduced into the cooling tube 110 (inner tube112) in a sprayed state.

In the direct cooling zone DC, a cooling tube may be used which has across-sectional area of the opening larger than that in the indirectcooling zone IC. As a result, the carrier gas that has passed throughthe indirect cooling zone IC can be rapidly expanded and the coolingefficiency can be increased.

In the drawings of the present specification, the specific coolingmechanism of the indirect cooling zone IC and direct cooling zone DC areomitted, but a well-known mechanism (for example, the mechanismdescribed in Japanese Translation of PCT International ApplicationPublication No. 2002-530521) can be used, provided that the operationeffect of the present invention is not impeded.

Further, protrusions or recesses may be provided in the inner wall ofthe inner tube 112 of the cooling tube 110 on the upstream side from thebelow-described virtual plane 120 b. As a result, the flow of the mixedgas of the carrier gas and metal vapor inside the cooling tube 110 isdisturbed and agitated. As a result, unevenness of the temperature andflow velocity of the carrier gas and the metal vapor concentration canbe suppressed, thereby better matching the timings of generation ofnuclei.

The carbon source supply unit 111 is connected to the opening, which isprovided locally in the inner wall of the inner tube 112, and providedsuch that the carbon source which is a source material for carboncoating in the carbon-coated metal powder can be supplied into theindirect cooling zone IC. The term “locally” used herein refers to aportion in the vicinity of the virtual plane 120 a which is preferably atransverse sectional zone with a width of 10 cm or less, more preferablya transverse sectional zone with a width of 5 cm or less in thelongitudinal direction of the cooling tube 110. In order to supply thecarbon source into the indirect cooling zone IC, it is preferred, forexample, that the size of the opening in the inner wall of the innertube 112 to which the carbon source supply unit 111 is connected be 10cm or less. In FIG. 1, only one opening is provided, but a plurality ofopenings may be provided and a carbon source may be supplied from aplurality of locations, provided that they are in the vicinity of thevirtual plane 120 a. For example, one more opening may be providedopposite the opening depicted in FIG. 1, and the carbon source may besupplied from the two openings.

As mentioned hereinabove, the carbon source supply unit 111 ispreferably provided such as to enable the supply of the carbon source inthe vicinity of the virtual plane 120 a, more preferably provided suchas to enable the supply of the carbon source to the upstream side fromthe virtual plane 120 a in the vicinity of the virtual plane 120 a. Thevirtual plane 120 a, as referred to herein, which is describedhereinbelow in greater detail, is the position where a large number ofmetal nuclei generate inside the indirect cooling zone IC when thecarbon source supply unit 111 is not provided, that is, when the carbonsource is not supplied to the indirect cooling zone IC. This virtualplane can be determined, for example, by simulating the temperaturedistribution inside the cooling tube 110 or analyzing the matter thathas adhered inside the cooling tube 110 of an actual device.

A collector (not depicted in the figure) is provided on the downstreamside from the cooling tube 110. The carbon-coated metal powder which hasbeen conveyed further downstream from the cooling tube 110 is separatedfrom the carrier gas and collected by the collector. The carrier gasseparated in the collector may be reused in the carrier gas supply unit106.

The plasma device 100 having a different configuration will be explainedhereinbelow with reference to FIG. 2. FIG. 2 is a schematic diagramillustrating another example of the configuration of the plasma device100 which is used in the method for manufacturing the carbon-coatedmetal powder in accordance with the present invention. Only the partsdifferent from those of the plasma device 100 depicted in FIG. 1 areexplained herein.

The indirect cooling zone IC is provided with a first indirect coolingzone 114 into which the metal vapor is conveyed from the reaction vessel101 and a second indirect cooling zone 115 which is disposed between thefirst indirect cooling zone 114 and the direct cooling zone DC. Thecross-sectional area of the opening of the first indirect cooling zone114 is less than the cross-sectional area of the opening of the secondindirect cooling zone 115. The opening, as referred to herein, is aportion serving as a flow channel in which the metal vapor is conveyed.In FIG. 2, the opening is a portion surrounded by the inner walls of theinner tubes 112 a, 112 b. The cross-sectional area, as referred toherein, is the area of the opening in a plane perpendicular to thelongitudinal direction of the cooling tube. It is preferred that thefirst indirect cooling zone 114 and the second indirect cooling zone 115each have a cylindrical shape and the inner diameter of the firstindirect cooling zone 114 be less than the inner diameter of the secondindirect cooling zone 115.

The carbon source supply unit 111 is preferably provided such as toenable the supply of the carbon source into the second indirect coolingzone 115, more preferably such as to enable the supply of the carbonsource into the second indirect cooling zone 115 in the vicinity of thefirst indirect cooling zone 114. In this case, the supply portion of thecarbon is a portion where the volume of the carrier gas rapidlyincreases and the concentration of the metal vapor rapidly decreasesafter or immediately after the metal vapor has been conveyed from thefirst indirect cooling zone 114 with a small cross-sectional area intothe second indirect cooling zone 115 with a large cross-sectional area.In the description hereinabove, the indirect cooling zone IC isconfigured of two zones of different cross-sectional areas, but it maybe also configured of three or more zones of different cross-sectionalareas.

The method for manufacturing the carbon-coated metal powder inaccordance with the present invention will be explained hereinbelow ingreater detail with reference to FIGS. 1 and 2. Described herein is themethod for manufacturing the carbon-coated metal powder which uses theabove-described plasma device 100, but the carbon-coated metal powdermay be also manufactured using a manufacturing device having anotherconfiguration.

[Metal Vapor Generation Step to Conveying Step]

Initially, the metallic raw material is introduced into the reactionvessel 101. The metallic raw material is not particularly limited,provided that it is an electrically conductive substance containingmetal components of the target carbon-coated metal powder. Pure metalsand also alloys, composites, mixtures, compounds, etc., containing twoor more metal components can be used. Examples of suitable metalcomponents include silver, gold, cadmium, cobalt, copper, iron, nickel,palladium, platinum, rhodium, ruthenium, tantalum, titanium, tungsten,zirconium, molybdenum, niobium, etc. The metallic raw materialpreferably has a boiling point higher than the decomposition temperatureof the carbon source, more preferably 700° C. to 3600° C. As a result,an atmosphere with a temperature equal to or higher than thedecomposition temperature of the carbon source can be easily obtainedinside the cooling tube 110. Where the boiling point is higher than3600° C., the carbon coating film is difficult to control.

The metallic raw material is not particularly limited, but base metalswhich are easier oxidized than noble metals are preferred because theeffect of the present invention is better demonstrated. A metallic rawmaterial containing at least either one of nickel and copper isparticularly preferred. It is particularly preferred that the metallicraw material consists essentially of nickel (boiling point 2732° C.)only, essentially of copper (boiling point 2567° C.) only, or a mixture,alloy, or composite of nickel and copper. “Consists essentially ofnickel only”, as referred to herein, means that nickel is contained inan amount of more than 98 wt. % in the metallic raw material. Likewise,“consists essentially of copper only”, as referred to herein, means thatcopper is contained in an amount of more than 98 wt. % in the metallicraw material. A nickel metallic raw material containing copper in anamount of 2 wt. % to 20 wt. % is particularly preferred as the metallicraw material containing nickel and copper. From the standpoint ofhandleability, it is preferred that a metal material, alloy, orcomposite material in the form of grains or lumps with a size of aboutseveral millimeters to several tens of millimeters be used as themetallic raw material, but such dimensions are not limiting.

The metallic raw material is heated and the metallic raw material ismelted and vaporized to generate a metal vapor. More specifically, theplasma 103 is generated between the cathode 104 and the anode 105, atleast part of the metallic raw material contained inside the reactionvessel 101 is melted by the heat of the plasma 103, and the melt 108 ofthe metallic raw material is generated. Part of the melt 108 isvaporized by the heat of the plasma 103 and the metal vapor isgenerated. It is preferred that the metal vapor generation step beimplemented in a state in which the carbon source is not present. Thus,it is preferred that the carbon source be not present inside thereaction vessel 101. This is because when the carbon source is presentin the reaction vessel 101, the carbon source is converted to plasma andthe coated amount of carbon is difficult to control. Further, heating byplasma is the preferred method for heating the metallic raw material,but this method is not limiting, provided that the metallic raw materialcan be melted and vaporized.

The metal vapor generated inside the reaction vessel 101 is conveyed bythe carrier gas into the cooling tube 110. It is preferred that an inertgas be used as the carrier gas. In the description hereinbelow, nitrogengas is used as the carrier gas, unless specifically stated otherwise. Ifnecessary, a reducing gas such as hydrogen, carbon monoxide, methane,ammonia gas or the like or organic compounds such as alcohols,carboxylic acids or the like may be mixed with the carrier gas. Inaddition, components such as phosphorus, sulfur or the like may beintroduced to improve and adjust the state and properties of thecarbon-coated metal powder. The plasma generating gas which has beenused for plasma generation also functions as part of the carrier gas. Asmentioned hereinabove, it is preferred that the carbon source be notpresent inside the reaction vessel 101, and it is preferred that gas notcontaining any component that can become a carbon source, such asmethane, be used as the carrier gas.

The flow rate of the carrier gas is preferably controlled such that themetal concentration becomes 0.01 g/L to 1 g/L. As a result, the metalvapor can be efficiently and rapidly cooled by endothermic decompositionof the carbon source.

[Metal Nuclei Generation Step]

The metal vapor conveyed from the reaction vessel 101 is cooled insidethe cooling tube 110, and metal nuclei generate from the metal vapor.The specific feature of the present invention is that the carbon sourcesupplied by the carbon source supply unit 111 into the cooling tube 110is endothermically decomposed and rapidly cools the metal vapor, therebyforming a carbon coating film on the surfaces of the metal nuclei inparallel with the generation of the metal nuclei.

The carbon source endothermically reacts during the decomposition(endothermically decomposes). The decomposition temperature of thecarbon source is preferably 700° C. to 3600° C. Where 3600° C. isexceeded, graphite contained in the carbon coating film formed on themetal surface easily sublimates and the carbon coating film is difficultto control.

Hydrocarbons such as ethane, methane, propane, butane, ethylene,propylene, butylene, etc., and alcohols such as ethanol, monoethyleneglycol, etc. can be used as the carbon source. The carbon source can bealso used in a solid, liquid, or gaseous form, but using a gaseouscarbon source is preferred. By using the gaseous carbon source, it ispossible to decompose the carbon source to carbon elements. Morespecifically, it is preferred that methane gas (decompositiontemperature about 700° C.) be used as the carbon source. It is alsopreferred that the decomposition temperature of the carbon source belower than the boiling temperature of the metallic raw materialpreferably by 100° C. or more, more preferably by 500° C. or more, evenmore preferably by 1000° C. or more, and it is preferred that nickel ora metallic raw material containing nickel as the main component be usedas the metallic raw material and methane gas be used as the carbonsource. As a result, the carbon source is efficiently decomposed at atemperature reached inside the cooling tube 110 where the metal vapor isconveyed. Where a mixed gas is supplied in which the carbon source isintroduced in a carrier gas such as argon gas, this mixed gas is alsoreferred to as “carbon source”.

Since the carbon source is endothermically decomposed, the metal vaporcan be cooled and metal nuclei can be generated even with a small amountof carbon source. Where the flow rate per minute is denoted by V (L) andthe cross-sectional area in the supply location of the carbon source isdenoted by S (cm²), the carbon source is supplied such that V/S (L/cm²)is greater than 0 and preferably 10 or less, more preferably 5 or less,even more preferably 3 or less. The temperature of the supplied carbonsource is not particularly limited, provided that it is less than thedecomposition temperature of the carbon source, and it is not necessaryto heat the carbon source in advance, and the carbon source, forexample, at room temperature (25° C. to 30° C.) can be used. The amountadded of the carbon source is preferably such as to obtain the carboncontent at 0.1 wt. % to 5 wt. % with respect to the amount of metal inthe generated carbon-coated metal powder. For example, it is preferredthat the flow rate of the carbon source be 7 L to 25 L per minute whennickel is used as the metallic raw material, a mixed gas in which 10%methane is included in an inert gas such as argon gas is used as thecarbon source, and the metal vapor concentration is 0.05 g/L.

The metal nuclei generation step is preferably performed in the indirectcooling step in which the above-mentioned metal vapor is indirectlycooled. The indirect cooling step can be performed in the indirectcooling zone IC of the cooling tube 110. In this step, the cooling fluidis neither sprayed into nor mixed with the metal vapor. Therefore, thecarbon source is easily supplied to the metal vapor present at aspecific position. Further, in the indirect cooling zone IC, the metalvapor in the carrier gas which is conveyed to the inside the coolingtube 110 in a high-temperature state is cooled by radiation cooling, andthe formation of the metal-coated carbon powder with uniform particlesize in the carrier gas is facilitated by advancing the growth andcrystallization of metal nuclei generated in the atmosphere with atemperature that is stably and uniformly controlled. Because of suchstable and uniform temperature control, the temperature of the metalvapor can be rapidly changed by the endothermic decomposition of thecarbon source.

More specifically, the metal vapor is conveyed from the reaction vessel101 to the indirect cooling zone IC of the cooling tube 110. At a pointof time at which the metal vapor in the carrier gas is introduced fromthe reaction vessel 101 into the indirect cooling zone IC, theconcentration of the metal vapor in the carrier gas is high and thetemperature is several thousand K (for example, 5000 K), but theindirect cooling (radiation cooling) reduces the temperature close tothe boiling point of the metal. Usually, where the metal vaportemperature becomes equal to or less than the boiling point, the metalvapor forms droplets and the generation of metal nuclei is started.Incidentally, a large number of nuclei start generating almost at thesame time at a certain position (in the present invention, called thevirtual plane) inside the indirect cooling zone IC. The virtual planechanges according to the types of the target metal and carbon source,concentrations of the metal vapor and carbon source, flow rate of thecarbon source and carrier gas, temperatures of the metal vapor, carriergas, and carbon source, and temperature distribution inside the coolingtube, etc. and does not indicate a specific position. However, in orderto facilitate the understanding, the virtual plane in the case thecarbon source is not supplied is set herein as 120 a and the virtualplane in the case the carbon source is supplied is set herein as 120 b.

In the present invention, the carbon source is supplied from the carbonsource supply unit 111 to the metal vapor which has been cooled to thevicinity of the boiling point. More specifically, it is preferred thatthe carbon source be supplied to a position (for example, the virtualplane 110 b) with a temperature equal to or higher than thedecomposition temperature of the carbon source and equal to or less than{(the boiling point of the metallic raw material)+[(the boilingpoint)×10%]}° C. For example, it is preferred that the carbon source besupplied to a position with a temperature equal to or higher than about700° C., which is the decomposition temperature of methane, and equal toor less than 3005° C. [2732° C. (boiling point of nickel)+(2732°C.×10%)].

In the plasma device 100 depicted in FIG. 1, the carbon source issupplied to the upstream side in the vicinity of the virtual plane 110a. This carbon source is heated to a temperature equal to or higher thanthe decomposition temperature, takes in the heat from the metal vapor bythe endothermic reaction proceeding when the carbon source isdecomposed, and rapidly cools the metal vapor. Since the temperaturerapidly decreases from the temperature around the boiling point, themetal vapor does not form droplets and becomes an unstable state(oversaturated state) even at a temperature equal to or lower than theboiling point. As a result of passing through such an oversaturatedstate, the generation of metal nuclei starts immediately. As aconsequence, the generation timings of metal nuclei are matched and theamount of metal nuclei is increased. Further, the carbon-coated metalpowder with a small particle size and narrow particle size distributionis obtained. The virtual plane 120 b is usually in the vicinity of theposition where the carbon source is supplied from the carbon sourcesupply unit 111, and in the plasma device depicted in FIG. 1, theupstream side in the vicinity of the virtual plane 120 a becomes thevirtual plane 120 b.

It is even more preferred that the indirect cooling step include a firstindirect cooling step and a second indirect cooling step in whichindirect cooling is performed in a state in which the concentration ofthe metal vapor attained in the first indirect cooling step has beenreduced. It is further preferred that in the second indirect coolingstep, the metal vapor be rapidly cooled by endothermic decomposition ofthe carbon source and that the formation of the carbon coating film onthe surfaces of metal nuclei be performed in parallel with thegeneration of metal nuclei. Further, since the volume of the metal vaporrapidly increases during the transition from the first indirect coolingstep to the second indirect cooling step, the effect of rapid cooling ofthe metal vapor can be further increased by additional cooling caused bysuch volume expansion. Thus, a state with a high degree ofoversaturation of the metal vapor concentration can be easily obtainedby rapidly cooling the metal vapor with the carbon source simultaneouslywith such additional rapid cooling. A higher degree of oversaturation ispreferred, and, in the case of transition metals such as nickel, copper,silver, etc., a state with a high degree of oversaturation isestablished by bringing the metal vapor temperature close to theirmelting point by rapid cooling.

In this case it is further preferred that the carbon source be suppliedto a position with a temperature equal to or higher than thedecomposition temperature of the carbon source and equal to or less than[(melting point of metallic raw material)+(melting point×25%)]° C. Forexample, where the carbon source is methane, it is further preferredthat the carbon source be supplied to a position with a temperatureequal to or higher than about 700° C., which is the decompositiontemperature of methane, to a temperature equal to or lower than 1816° C.[(1453° C., which is the melting point of nickel)+(1453° C.×25%)].

The first indirect cooling step and second indirect cooling step can berealized using the plasma device depicted in FIG. 2. Initially, indirectcooling is performed in a state with a high concentration of metal vaporin the first indirect cooling zone 114 and then indirect cooling iscontinuously performed in a state with a reduced concentration of metalvapor in the second indirect cooling zone 115. The carbon source issupplied by the carbon source supply unit 111 in the second indirectcooling zone 115, preferably in the second indirect cooling zone 115 inthe vicinity of the first indirect cooling zone 114. In this case, thevirtual planes 120 a and 120 b are almost at the same position, forexample, at a position in the second indirect cooling zone 115 in thevicinity of the first indirect cooling zone 114.

The carbon source decomposition product (carbon) is present around themetal vapor immediately before the metal nuclei are generated and aroundthe metal nuclei immediately after the generation thereof. Therefore,the formation of carbon coating film on the surfaces of the metal nucleiis started almost simultaneously with the generation of the metal nucleior somewhat later, but still immediately after the generation of themetal nuclei. Further, since the coating is formed by the carbon formedby thermal decomposition, rather than carbon converted into plasma, acarbon-coated metal powder can be obtained in which a substantiallyuniform carbon coating film is formed.

[Nuclei Growth Step to Collection Step]

As mentioned hereinabove, the generated metal nuclei are continuouslysubjected to grain growth and crystallization in the indirect coolingzone IC. The grain growth generally involves the grain growth advancingas a result of deposition of the metal vapor surrounding the nuclei onthe nuclei surfaces and the grain growth advancing as a result ofcoalescence of a plurality of adjacent nuclei, and the latter mechanismis apparently predominant in terms of the effect produced on the widthof particle size distribution. In the present invention, the carboncoating film is formed on the surfaces of metal nuclei substantiallysimultaneously with the generation of the metal nuclei or somewhatlater, but still immediately after the generation of the metal nuclei.Therefore the grain growth by coalescence is suppressed. As a result, itis possible to obtain a carbon-coated metal powder with a uniformparticle size and a very narrow particle size distribution.

The carbon-coated metal powder generated by indirect cooling in theindirect cooling zone IC is then directly cooled in the direct coolingzone DC. The carbon-coated metal powder which has been directly cooledin the direct cooling zone DC is conveyed further downstream from thecooling tube 110 and separated from the carrier gas and collected in thecollector.

[Heat Treatment Step]

The collected carbon-coated metal powder is preferably subjected to heattreatment. As a result, the degree of crystallinity of graphite in thecarbon coating is increased and the sintering suppression effect isenhanced. The degree of crystallinity of graphite can be evaluated by apeak intensity derived from the G band of graphite in Raman spectroscopymeasurement. It is preferred that the half-value width of the G bandpeak be 100 or less. Where it is above 100, the carbon coating is in astate in which a large amount of an amorphous component remains and thedegree of crystallinity is insufficient.

The heat treatment is implemented, for example, for one hour to 10 hoursat 180° C. to 1000° C. under an inert atmosphere, or for one hour to 10hours at 180° C. to 400° C. under an air atmosphere. The preferred heattreatment temperature is 180° C. to 300° C. Where the heat treatmenttemperature is above 300° C., thermal aggregation occurs anddispersivity is degraded. Where the heat treatment temperature is lowerthan 180° C., the degree of crystallinity of graphite decreases and theeffect produced by the heat treatment is reduced.

The carbon-coated metal powder obtained by the method for manufacturinga carbon-coated metal powder in accordance with the present inventionhas a small particle size and a narrow particle size distribution.Further, since the carbon coating film is not formed after the metalpowder has been formed, as in the conventional methods, and theformation of the carbon coating film advances simultaneously with theformation of the metal powder, the amount of impurities in the obtainedcarbon-coated metal powder can be reduced. The impurities, as referredto herein, are components that are unavoidably admixed from the startingmaterials, in the manufacturing step, etc., rather than components thatare introduced intentionally. Usually, the impurities are chlorine,alkali metals, etc. Therefore, where components such as phosphorus,sulfur, etc. are introduced, for example, into the carrier gas, forimproving and adjusting the state and properties of the carbon-coatedmetal powder, those components are not referred to as impurities. Thecontent of impurities is preferably 3 wt. % or less, the specific valuedepending on the particle size. With the manufacturing method inaccordance with the present invention, the carbon-coated metal powder inaccordance with the present invention which has a good carbon coatingfilm can be easily obtained.

[Conductive Paste and Multilayer Electronic Component Using the Same]

The conductive paste in accordance with the present invention includesthe above-described carbon-coated metal powder as an electricallyconductive powder, the powder being kneaded with a vehicle constitutedby a solvent and a binder resin. The conductive paste can beparticularly advantageously used for forming internal conductors(internal electrodes) of multilayer electronic components such asmultilayer capacitors, multilayer inductors, multilayer actuators, etc.but can be also used for forming terminal electrodes of ceramicelectronic components and thick-film conductor circuits. Thecarbon-coated metal powder may be the carbon-coated metal powdercharacterized by TMA properties, etc. or the carbon-coated nickel-basedpowder characterized by ESCA analysis.

An example of a method for manufacturing the conductive paste and amultilayer electronic component will be described hereinbelow.

Initially, the carbon-coated metal powder in accordance with the presentinvention, a binder resin, and a solvent are kneaded using a three-rollmill. As the binder resin, cellulose resins such as ethyl cellulose,hydroxyethyl cellulose, etc., acrylic resins, methacrylic resins,butyral resins, epoxy resins, phenolic resins, rosin and so forth can bementioned and the binder resin usually can be mixed in about 1 part byweight to 15 parts by weight per 100 parts by weight of the conductivepower. As the solvent, organic solvents such as alcohols such asdihydroterpineol, etc., ketones, ethers, esters, hydrocarbons, etc., andwater, or mixed solvents thereof can be selected for use as appropriate.The solvent is mixed in an appropriate amount correspondingly to theproperties of the conductive powder, type of resin, applying method, andso forth. Usually, the amount of solvent is about 40 parts by weight to150 parts by weight per 100 parts by weight of the conductive powder.

In addition to the above-mentioned components, the conductive paste ofthe present invention may suitably contain other commonly blendedcomponents in accordance with the intended use, examples of whichinclude a ceramic that is the same as the ceramic contained in theceramic sheet or that has a similar composition thereto, as well asglass, alumina, silica, copper oxide, manganese oxide, titanium oxideand other metal oxides, montmorillonite and other inorganic powders,organometallic compounds, a plasticizer, a dispersant, a surfactant,etc.

The conductive paste is manufactured in the above-described manner.

Then, the electrically conductive paste is printed in predeterminedpatterns on unfired ceramic green sheets serving as unfired ceramiclayers, the solvent is removed by drying, and internal conductor pastelayers are formed. A plurality of the obtained unfired ceramic greensheets having the internal conductor paste layer are stacked and bondedtogether under pressure to obtain an unfired multilayer body in whichthe unfired ceramic green sheets and internal conductor paste layers arestacked alternately.

The multilayer body is cut to a predetermined shape and then subjectedto a binder removal step to burn out and dissipate the binder resin. Theinternal conductor layers are then formed simultaneously with sinteringof the ceramic layers by firing the multilayer body at a hightemperature of about 1200° C. to 1400° C., and a ceramic element body isobtained. A multilayer electronic component is then obtained by printingterminal electrodes onto both end surfaces of the element body. Theterminal electrodes may be formed by coating a conductive paste for endterminals onto both end surfaces of the above-mentioned unfiredmultilayer body which has been cut to the predetermined shape, and thenfiring the paste simultaneously with the multilayer body.

By using the carbon-coated metal powder containing few impurities, it ispossible to prevent the generation of gases during firing and obtaingood fired film (internal conductor layer). Further, since thecarbon-coated metal powder has good carbon coating film, the dispersionof the powder in the conductive paste is enhanced and shrinkageproperties during sintering are improved thereby bringing the sinteringshrinkage behaviors of the conductor layers and ceramic layers close toeach other and suppressing the occurrence of cracks and delamination.

Further, since the carbon-coated metal powder in accordance with thepresent invention has a narrow particle size distribution and a smallaverage particle size, even when the fired film formed by coating andfiring the conductive paste containing the carbon-coated metal powderhas a small thickness, the film has few holes (defects) and excels insmoothness, denseness, and continuity, and the internal conductor layerscan be reduced in thickness. The thickness of the internal conductorlayers is, for example, 0.4 μm to 0.8 μm.

It follows from the above, that when the conductive paste containing thecarbon-coated metal powder in accordance with the present invention isused for manufacturing a multilayer electronic component, a multilayerelectronic component provided with thin internal conductor layers, whichexcel in denseness and continuity, and having excellent properties canbe obtained without generating structural defects such as cracks,delamination, etc.

EXAMPLES

The present invention will be specifically described hereinbelow on thebasis of examples thereof, but the present invention is not limited tothose examples.

Example 1

A carbon-coated metal powder was manufactured using the plasma device100 depicted in FIG. 2. A tube having a combination of an inner tube 112a (first indirect cooling zone 114) with an inner diameter of 3.8 cm, aninner tube 112 b (second indirect cooling zone 115) with an innerdiameter of 8 cm, and an inner tube 112 c (direct cooling zone DC) withan inner diameter of 15 cm was used as the cooling tube 110. The lengthof the inner tube 112 a was 20 cm, the length of the inner tube 112 bwas 22.5 cm, and the length of the inner tube 112 c was 20 cm. A carbonsource was supplied from a carbon source supply unit 111 having an innerdiameter (supply port) of 0.32 cm at a position apart by 5 cm from theupstream end of the second indirect cooling zone 115 in the downstreamdirection. The plasma device having the above-described configuration isreferred to as plasma device A.

Nickel was used as the metallic raw material, and the vaporization ratewas 10 g per minute. Nitrogen gas was used as the carrier gas. The flowrate of the carrier gas passing through the cooling tube was 200 L perminute, and the metal concentration was controlled to 0.05 g/L. A mixedgas (referred to hereinbelow as 10% methane gas) containing 10% methanein an argon gas (carrier gas) was used as the carbon source, the supplyrate was 25 L per minute, and the temperature of the supplied carbonsource was room temperature (25° C. to 30° C.)

In a state in which the carbon source was supplied and the metal vaporwas conveyed, the temperature T_(β) at a position (usually, in thevicinity of the virtual plane 120 a) at which the carbon source wassupplied was 1040° C. Further, in a state in which the metal vapor wasconveyed without supplying the carbon source, the temperature at thisposition was the temperature T_(α) of 1100° C.

Unless otherwise specified, in the examples below, the temperature atthe position (usually, in the vicinity of the virtual plane 120 a) wherea carbon source (in Comparative Examples 1 and 2, a nitrogen gas wasused instead of the 10% methane gas) was supplied to the cooling tube ina state in which the metal vapor is conveyed was taken as T_(β), and thetemperature at the same position as the T_(β) measurement position in astate in which the metal vapor was conveyed without supplying a carbonsource (in Comparative Examples 1 and 2, without supplying a nitrogengas used instead of the 10% methane gas) into the cooling tube was takenas T_(α).

Example 2

The experiment was performed in the same manner as in Example 1, exceptthat the flow rate of the carbon source was 7 L per minute. T_(α) was1100° C. and T_(β) was 1050° C.

Example 3

The experiment was performed in the same manner as in Example 1, exceptthat the flow rate of the carbon source was 6 L per minute. T_(α) was1100° C. and T_(β) was 1050° C.

Example 4

The experiment was performed in the same manner as in Example 1, exceptthat the flow rate of the carbon source was 40 L per minute. T_(α) was1100° C. and T_(β) was 1024° C.

Example 5

The experiment was performed in the same manner as in Example 1, exceptthat a mixed gas containing 3% propane in an argon gas was used as thecarbon source. T_(α) was 1100° C. and T_(β) was 1035° C.

Example 6

A carbon-coated metal powder was manufactured using the plasma device A.Silver was used as the metallic raw material, and the vaporization ratewas 100 g per minute. Nitrogen gas was used as the carrier gas. Thecarrier gas was flowed through the cooling tube at 200 L per minute, andthe metal concentration was controlled to 0.5 g/L. The 10% methane gaswas used as the carbon source, the supply rate was 25 L per minute, andthe temperature of the supplied carbon source was room temperature (25°C. to 30° C.). T_(α) was 750° C. and T_(β) was 700° C.

Example 7

A carbon-coated metal powder was manufactured using the plasma device A.Copper was used as the metallic raw material, and the vaporization ratewas 15 g per minute. Nitrogen gas was used as the carrier gas. Thecarrier gas was flowed through the cooling tube at 200 L per minute, andthe metal concentration was controlled to 0.075 g/L. The 10% methane gaswas used as the carbon source, the supply rate was 25 L per minute, andthe temperature of the supplied carbon source was room temperature (25°C. to 30° C.). T_(α) was 920° C. and T_(β) was 880° C.

Example 8

A carbon-coated metal powder was manufactured using the plasma device A.An alloy of nickel and copper (the content of copper was 2 wt. %) wasused as the metallic raw material, and the vaporization rate was 10 gper minute. Nitrogen gas was used as the carrier gas. The carrier gaswas flowed through the cooling tube at 200 L per minute, and the metalconcentration was controlled to 0.05 g/L. The 10% methane gas was usedas the carbon source, the supply rate was 25 L per minute, and thetemperature of the supplied carbon source was room temperature (25° C.to 30° C.). T_(α) was 1080° C. and T_(β) was 1035° C.

Example 9

A carbon-coated metal powder was manufactured using the plasma device A.An alloy of nickel and copper (content ratio of copper was 20 wt. %) wasused as the metallic raw material, and the vaporization rate was 12 gper minute. Nitrogen gas was used as the carrier gas. The carrier gaswas flowed through the cooling tube at 200 L per minute, and the metalconcentration was controlled to 0.06 g/L. The 10% methane gas was usedas the carbon source, the supply rate was 25 L per minute, and thetemperature of the supplied carbon source was room temperature (25° C.to 30° C.). T_(α) was 1075° C. and T_(β) was 1020° C.

Example 10

A carbon-coated metal powder was manufactured using the plasma device100 depicted in FIG. 2. A tube having a combination of an inner tube 112a (first indirect cooling zone 114) with an inner diameter of 8.9 cm, aninner tube 112 b (second indirect cooling zone 115) with an innerdiameter of 10.3 cm, and an inner tube 112 c (direct cooling zone DC)with an inner diameter of 22 cm was used as the cooling tube 110. Thelength of the inner tube 112 a was 3.5 cm, the length of the inner tube112 b was 46 cm, and the length of the inner tube 112 c was 42.3 cm. Acarbon source was supplied from the carbon source supply unit 111 havingan inner diameter (supply port) of 1 cm at a position apart by 10 cmfrom the upstream end of the second indirect cooling zone 115 in thedownstream direction. The plasma device having the above-describedconfiguration is referred to as plasma device B.

Nickel was used as the metallic raw material, and the vaporization ratewas 85 g per minute. Nitrogen gas was used as the carrier gas. Thecarrier gas was flowed through the cooling tube at 750 L per minute, andthe metal concentration was controlled to 0.11 g/L. The 10% methane gaswas used as the carbon source, the supply rate was 20 L per minute, andthe temperature of the supplied carbon source was room temperature (25°C. to 30° C.). T_(α) was 1780° C. and T_(β) was 1500° C.

Example 11

A carbon-coated metal powder was manufactured using the plasma device B.Nickel was used as the metallic raw material, and the vaporization ratewas 50 g per minute. Nitrogen gas was used as the carrier gas. Thecarrier gas was flowed through the cooling tube at 750 L per minute, andthe metal concentration was controlled to 0.07 g/L. A mixed gascontaining 3% methane in an argon gas was used as the carbon source, thesupply rate was 103 L per minute, and the temperature of the suppliedcarbon source was room temperature (25° C. to 30° C.). T_(α) was 1650°C. and T_(β) was 1380° C.

Example 12

A carbon-coated metal powder was manufactured using the plasma device100 depicted in FIG. 2. A tube having a combination of an inner tube 112a (first indirect cooling zone 114) with an inner diameter of 8.9 cm, aninner tube 112 b (second indirect cooling zone 115) with an innerdiameter of 22 cm, and an inner tube 112 c (direct cooling zone DC) withan inner diameter of 22 cm was used as the cooling tube 110. The lengthof the inner tube 112 a was 10.3 cm, the length of the inner tube 112 bwas 22.5 cm, and the length of the inner tube 112 c was 44.3 cm. Acarbon source was supplied from the carbon source supply unit 111 havingan inner diameter (supply port) of 1 cm at a position apart by 11 cmfrom the upstream end of the second indirect cooling zone 115 in thedownstream direction.

Nickel was used as the metallic raw material, and the vaporization ratewas 85 g per minute. Nitrogen gas was used as the carrier gas. Thecarrier gas was flowed through the cooling tube at 750 L per minute, andthe metal concentration was controlled to 0.11 g/L. The 10% methane gaswas used as the carbon source, the supply rate was 20 L per minute, andthe temperature of the supplied carbon source was room temperature (25°C. to 30° C.). T_(α) was 1780° C. and T_(β) was 1470° C.

Example 13

A carbon-coated metal powder was manufactured using the plasma device100 depicted in FIG. 2. A tube having a combination of an inner tube 112a (first indirect cooling zone 114) with an inner diameter of 10.3 cm,an inner tube 112 b (second indirect cooling zone 115) with an innerdiameter of 12.8 cm, and an inner tube 112 c (direct cooling zone DC)with an inner diameter of 36.9 cm was used as the cooling tube 110. Thelength of the inner tube 112 a was 24.5 cm, the length of the inner tube112 b was 45 cm, and the length of the inner tube 112 c was 54.7 cm. Acarbon source was supplied from the carbon source supply unit 111 havingan inner diameter (supply port) of 1.9 cm at a location apart by 10 cmfrom the upstream end of the second indirect cooling zone 115 in thedownstream direction.

Nickel was used as the metallic raw material, and the vaporization ratewas 85 g per minute. Nitrogen gas was used as the carrier gas. Thecarrier gas was flowed through the cooling tube was 850 L per minute,and the metal concentration was controlled to 0.10 g/L. The 10% methanegas was used as the carbon source, the supply rate was 20 L per minute,and the temperature of the supplied carbon source was room temperature(25° C. to 30° C.). T_(α) was 1620° C. and T_(β) was 1340° C.

Comparative Example 1

The experiment was performed in the same manner as in Example 1, exceptthat nitrogen gas was used instead of the carbon source (10% methanegas) as a supplied material from the carbon source supply unit 111.T_(α) and T_(β) each were 1100° C.

Comparative Example 2

The experiment was performed in the same manner as in Example 6, exceptthat the carbon source supply unit 111 was provided to the directcooling zone DC, rather than to the second indirect cooling zone 115,and nitrogen gas was supplied instead of the carbon source (10% methanegas) into the direct cooling zone DC. T_(α) and T_(β) each were 350° C.

Comparative Example 3

The experiment was performed in the same manner as in Example 1, exceptthat the carbon source supply unit 111 was provided to the reactionvessel 101, rather than to the second indirect cooling zone 115, and thecarbon source was supplied into the reaction vessel 101. As mentionedhereinabove, at a point of time at which the metal vapor in the carriergas is introduced from the reaction vessel 101 into the indirect coolingzone IC, the temperature is, for example, 5000 K. Therefore, T_(α) canbe assumed to be equal to or higher than 5000 K. Further, since theinterior of the reaction vessel 101 is continuously heated, T_(β) alsocan be assumed to be equal to or higher than 5000 K.

Comparative Example 4

The experiment was performed in the same manner as in Example 1, exceptthat the carbon source supply unit 111 was provided to the directcooling zone DC, rather than to the second indirect cooling zone 115,and the carbon source was supplied into the direct cooling zone DC.T_(α) and T_(β) each were 350° C.

Comparative Example 5

The experiment was performed in the same manner as in Example 1, exceptthat the carbon source supply unit 111 was not provided, that is, thecarbon source was not supplied. The temperature at the location whereT_(α) and T_(β) were measured in Example 1 was 1100° C.

[Evaluation of Carbon-Coated Metal Powder]

The average particle size, SD value, carbon content, contents ofimpurities, and thickness of carbon coating film were determined foreach of the carbon-coated metal powders obtained in Examples 1 to 13 andComparative Examples 1 to 5. The contents of oxygen, sulfur, andchlorine were determined as the contents of impurities. The results areshown in Table 1.

TABLE 1 Contents of impurities Oxygen content Average Specific perspecific Thickness particle surface Carbon Oxygen surface area of SulfurChlorine of carbon size area content content 1 m²/g content contentcoating film (nm) SD value (m²/g) (wt. %) (wt. %) (ppm) (wt. %) (wt. %)(nm) Example 1 190 0.88 8.83 2.68 0.25 283 N.D N.D. 10 Example 2 2600.92 5.1 1.20 0.01 20 N.D. N.D. 5 Example 3 260 1.05 6.63 0.83 0.19 287N.D. N.D. 4 Example 4 220 0.97 6.45 3.40 0.49 760 N.D. N.D. 14 Example 5200 0.94 7.14 1.22 0.17 238 N.D. N.D. 5 Example 6 180 0.96 3.1 3.20 0.0265 N.D. N.D. 6 Example 7 290 0.98 2.56 1.80 0.28 1094 N.D. N.D. 9Example 8 210 0.96 6.98 1.52 0.22 315 N.D. N.D. 11 Example 9 235 0.966.97 1.61 0.21 301 N.D. N.D. 11 Example 10 218 1.09 4.47 1.80 0.04 89N.D. N.D. 8 Example 11 183 1.13 5.51 2.22 0.17 309 N.D. N.D. 9 Example12 220 1.15 8.09 1.85 0.05 62 N.D. N.D. 8 Example 13 212 1.07 5.24 1.780.06 115 N.D. N.D. 8 Comparative 330 1.51 4.53 N.D. 1.80 3974 N.D. N.D.N.D. Example 1 Comparative 200 Unmeasurable — N.D. 0.13 — N.D. N.D. N.D.Example 2 because of considerable aggregation Comparative 322 1.54 4.953.40 0.29 586 N.D. N.D. 11 Example 3 Comparative 336 1.53 5.05 0.12 1.683327 N.D. N.D. N.D. Example 4 Comparative 341 1.58 5.02 N.D. 1.80 3586N.D. N.D. N.D. Example 5 N.D.: Non-detectable

The average particle size and SD value were determined in the followingmanner. The 10% value, 50% value, and 90% value (referred to hereinbelowas “D10”, “D50”, and “D90”, respectively) in the volume-based cumulativefraction in the particle size distribution measured using a laserdiffraction type particle size distribution analyzer (LA-920,manufactured by HORIBA, Ltd.) were determined for the obtainedcarbon-coated metal powders. The average particle size refers to D50.Further, (D90−D10)/(D50) was determined as an indicator of particle sizedistribution and taken as the SD value. The content of carbon andcontent of sulfur were measured using a carbon/sulfur analyzer(EMIA-320V, manufactured by HORIBA, Ltd.). The content of oxygen wasmeasured using a nitrogen/oxygen analyzer (EMGA-920, manufactured byHORIBA, Ltd.). The content of chlorine was measured by a titrationmethod.

The thickness of the carbon coating film was determined from theobservation image of the carbon-coated metal powder which was observedunder a TEM (HD-2000, manufactured by HITACHI, Ltd.). FIG. 3 is a TEMimage of the carbon-coated metal powder of Example 1. In FIG. 3, a darkportion is the metal particles 10 and a somewhat light portion is thecarbon coating film 11. The thickness of the carbon coating film 11 is alength from the boundary between the dark portion and the light portionto the outer circumference of the light portion (in FIG. 3, the lengthof the portion shown by an arrow). In Table 1 the average value obtainedby measuring the lengths at 20 random locations for one particle ispresented as “thickness of carbon coating film”.

The TMA shrinkage percentages were also determined for the carbon-coatedmetal powders of Examples 1 to 5 and 8 to 13 and Comparative Examples 1and 3 to 5. The results are shown in Table 2. The TMA charts obtained bymeasurements in Examples 1 to 5, 8, and 11 and Comparative Examples 1and 3 to 5 are shown in FIGS. 4 and 5.

TABLE 2 Temperature width of 200° C. X′_(MAX) X_(MAX) (%) Temperaturerange (° C.) X_(200° C) (%) X (%) (%) X′ (%) Example 1 6.801000.0-1200.0 2.07 30.4 1.01 14.8 Example 2 15.0 650.0-850.0 4.93 32.91.64 11.0 Example 3 19.2 599.9-799.9 7.79 40.6 3.26 17.0 Example 4 6.71599.9-799.9 1.96 29.2 0.90 13.5 Example 5 12.8 700.0-900.0 5.15 40.21.26 9.9 Example 8 12.2 700.0-900.0 5.14 42.1 1.92 15.8 Example 9 16.3450.1-650.1 4.69 28.8 2.83 17.3 Example 10 6.42 700.0-900.0 2.21 34.41.12 17.5 Example 11 3.73 737.4-937.4 1.07 28.7 0.77 20.8 Example 126.71 550.0-750.0 2.18 32.5 0.90 13.5 Example 13 6.95 1000.0-1200.0 2.7339.3 0.63 9.01 Comparative 17.7 467.7-667.7 10.6 59.9 6.23 35.2 Example1 Comparative 5.74 220.0-420.0 1.81 31.6 2.22 38.7 Example 3 Comparative18.3 390.0-590.0 12.2 66.7 6.57 35.9 Example 4 Comparative 19.5400.0-600.0 11.9 61.0 7.51 38.5 Example 5

The TMA shrinkage percentage was determined in the following manner. ATMA device (TMA4000S manufactured by BRUKER Corporation) was used forthe measurements. A carbon-coated metal powder molded in a columnarshape with a diameter of 5 mm and a height of about 2 mm was used as asample, the temperature was raised from room temperature to 1300° C. (inExample 8, to 1200° C.) at a rate of 5° C./rain in a nitrogen gascontaining 4% of hydrogen, and the shrinkage percentage in the heightdirection of the sample was measured. In FIGS. 4 and 5, the shrinkagepercentage (%) is a size variation percentage (%) in the heightdirection of the sample with respect to rising temperature. The negativevalue indicates shrinkage. The higher is the absolute value of thenegative value, the larger is the shrinkage percentage (%).

Further, the shift amount of the peak position attributable to 1 s of acarbon atom from the particle surface toward the particle center wasalso determined by surface analysis by ESCA with respect to powders ofExamples 1 to 5 and 8 to 13 and Comparative Examples 3 and 4. InComparative Examples 1 and 5, carbon was not detected, as indicated inTable 1. Therefore, the surface analysis by ESCA in the vicinity of thepeak position attributable to 1 s of a carbon atom was not performed.The results obtained are shown in Table 3. The results of surfaceanalysis by ESCA relating to Examples 5, 8, and 11 and ComparativeExample 3 are shown in FIGS. 6 to 9. FIGS. 6 to 9 show how argon ionetching changes the intensity of the is peak of carbon measured in abinding energy range of 276 eV to 294 eV.

TABLE 3 Shift Binding Energy(eV) amount Etching amount 1 nm Etchingamount 11 nm (eV) Example 1 284.662 284.456 −0.206 Example 2 284.730284.452 −0.278 Example 3 284.817 284.517 −0.300 Example 4 285.351284.849 −0.502 Example 5 284.871 284.547 −0.324 Example 8 284.759284.488 −0.271 Example 9 284.877 284.654 −0.223 Example 10 284.652284.478 −0.174 Example 11 284.526 284.326 −0.200 Example 12 284.834284.652 −0.182 Example 13 284.704 284.604 −0.100 Comparative 284.569284.593 0.024 Example 3 Comparative 284.454 284.500 0.046 Example 4

The shift amount of the peak position was determined in the followingmanner. ESCA (ESCA-3400, manufactured by SHIMADZU Corporation) was usedfor measurements, and an Mg-Kα beam (1250 eV) was used as an incidentX-ray source. The peak positions at etching depths of 1 nm and 11 nmwere studied while performing argon ion etching, and the differencetherebetween (shift amount) was determined. Where the shift amount is anegative value in Table 3, it means that the peak position at theetching depth of 11 nm has shifted to the low-energy side with respectto the peak position at an etching depth of 1 nm. Conversely, when theshift amount takes a positive value, it means that the shift is to thehigh-energy side.

The presence/absence of peaks attributable to nickel oxide and nickelhydroxide was also studied with respect to the powders of Examples 1 to5 and 8 to 13 and Comparative Examples 1 and 3 to 5. The surfaceanalysis results measured by ESCA within a binding energy range of 850eV to 880 eV with respect to the powders of Examples 5, 8, and 11 aredepicted in FIGS. 10 to 12. ESCA (ESCA-3400, manufactured by SHIMADZUCorporation) was used for measurements, and an Mg-Kα beam (1250 eV) wasused as an incident X-ray source, in the same manner as describedhereinabove.

SEM observations (SU-8020 manufactured by HITACHI, Ltd.) were alsoperformed with respect to the powders of Example 1 and ComparativeExample 3. FIGS. 13 and 14 show SEM images of carbon-coated metalpowders obtained in Example 1 and Comparative Example 3, respectively.

The continuity of the fired film (coverage percentage of the fired film)and smoothness (surface roughness of the dry paste film) were evaluatedwith respect to the carbon-coated metal powder obtained in Example 1,the same powder subjected to heat treatment (Examples 1-1 to 1-4), andthe carbon-coated metal powder obtained in Comparative Examples 3 and 5.The results are shown in Table 4.

TABLE 4 Coverage percentage Surface roughness of of fired film (%) drypaste film Ra/Rz (nm) Example 1 93 14/144 Example 1-1 98 16/138 Example1-2 98 16/142 Example 1-3 97 17/138 Example 1-4 94 28/151 Comparative 9033/256 Example 3 Comparative 42 37/270 Example 5

The evaluations were performed in the following manner. A total of 100parts by weight of the carbon-coated metal powder, 5 parts by weight ofethyl cellulose, and 95 parts by weight of dihydroterpineol were mixed,and kneaded using a three-roll mill to fabricate a conductive paste. Theobtained conductive paste was coated on an alumina substrate to obtain afilm thickness after firing of about 1 μm and fired at 1200° C. in a 1%H₂/N₂ atmosphere.

In Example 1-1, a carbon-coated metal powder was used that was obtainedby subjecting the carbon-coated metal powder obtained in Example 1 toheat treatment for 2 hours at 180° C. under the air atmosphere. InExample 1-2, a carbon-coated metal powder was used that was obtained bysubjecting the carbon-coated metal powder obtained in Example 1 to heattreatment for 10 hours at 180° C. under the air atmosphere. In Example1-3, a carbon-coated metal powder was used that was obtained bysubjecting the carbon-coated metal powder obtained in Example 1 to heattreatment for 2 hours at 300° C. under the air atmosphere. In Example1-4, a carbon-coated metal powder was used that was obtained bysubjecting the carbon-coated metal powder obtained in Example 1 to heattreatment for 2 hours at 1000° C. under the nitrogen atmosphere.

The fired films were observed with a SEM (SU-8020, manufactured byHITACHI, Ltd.), and the surface area ratio of the metal film and aportion where the metal film is not present in the specific surface areawas evaluated as a continuity of the fired film. FIGS. 15 and 16 showSEM images of fired films obtained by using the carbon-coated metalpowder obtained in Examples 1 and 1-1, and FIGS. 17 and 18 shows theimages obtained in Comparative Examples 3 and 5.

Further, the conductive paste was coated on an alumina substrate such asto obtain a film thickness after drying of about 1 μm and dried for 2hours at 150° C. under the air atmosphere. The surface roughness (Ravalue and Rz value) of the dry paste film was determined using a surfaceroughness meter (SURFCORDER ET3000, manufactured by KOSAKA LABORATORYLtd.). The surface roughness Ra and Rz shown in Table 4 are thearithmetic average roughness and ten-point average roughness stipulatedby JIS B 0601-1994.

CONCLUSION

The above-described results demonstrate that the manufacturing method inaccordance with the present invention makes it possible to obtain acarbon-coated metal powder with few impurities and a narrow particlesize distribution. More specifically, comparing Example 1 withComparative Example 5, which was the same as Example 1, except that nocarbon source was supplied, it is clear that in Example 1 the content ofoxygen was lower, the average particle size was less, and the SD valuewas less than in the comparative example. The same trend was alsoobserved in comparing Example 1 with Comparative Example 1, in which amaterial other than the carbon source was supplied from the carbonsource supply unit 111. The comparison of FIGS. 13 and 14 alsodemonstrates that in Example 1 the particle size was less and theparticle size distribution was narrower than in Comparative Example 3.

Further, referring to FIG. 5, it is clear that in Comparative Examples1, 4, and 5 in which the carbon coating film was not formed, rapidshrinkage started from a certain temperature and the shrinkagepercentage became constant from about 600° C. Thus, it was found that inComparative Examples 1, 4, and 5, an inflection point A appeared in thevicinity of 600° C. In other words, in Comparative Examples 1, 4, and 5,the sintering end temperature was in the vicinity of 600° C. Further,referring to FIG. 4, it is clear that in Examples 1 to 5, 8, and 11 inwhich the carbon coating film was formed, shrinkage gradually proceededafter the sintering had started, and the inflection point did not appearat least till a firing temperature (in this case, 1200° C.) of theconductive paste containing the carbon-coated metal powder obtained inExamples 1 to 5, 8, and 11. Since no rapid shrinkage thus occurred tillthe firing temperature, the fired film obtained by coating and firingthe conductive paste containing the carbon-coated metal powder inaccordance with the present invention had few holes (defects) andexcelled in smoothness and denseness. This is also clear from theresults shown in Table 4 and FIGS. 15 to 18.

It also follows from the results shown in Table 3, that in Examples 1 to5 and 8 to 13, the shift amount had a negative value and the shift wasto the low-energy side. In Comparative Examples 3 and 4, the shiftamount had positive value and the shift was to the high-energy side.Thus, in Comparative Examples 3 and 4, the nickel carbide layer wasapparently practically not present.

Further, in Examples 1 to 5 and 8 to 13, peaks attributable to nickeloxide and nickel hydroxide were not present. In Comparative Examples 1,4, and 5, peaks attributable to nickel oxide and nickel hydroxide werepresent.

Thus, in Examples 1 to 5 and 8 to 13, the surface state of the particlesof the carbon-coated metal powder was good. Therefore, the improvementof shrinkage characteristic is sufficient, and when the conductive pastecontaining such carbon-coated metal powder is used for forming aninternal conductor in a multilayer ceramic configuration, it is possibleto obtain a multilayer electronic component, which has a thin internalconductor layer that excels in denseness and continuity, and hasexcellent characteristics, without generating structural defects such ascracks and delamination. Further, as a result of forming a continuouscarbon-coated layer, with nickel carbide being interposed, it isunlikely that physical forces acting during paste kneading, or the like,can cause defects such as peeling of the coating layer, etc. However,where the carbide interlayer is not present, adhesion at the interfaceof nickel and coating layer is insufficient, defects are easily causedby mechanical forces, and the carbon coating cannot demonstrate asufficient effect.

REFERENCE SIGNS LIST

-   -   10 metal particle    -   11 carbon coating film    -   100 plasma device    -   101 reaction vessel    -   102 plasma torch    -   103 plasma    -   104 cathode    -   105 anode    -   106 carrier gas supply unit    -   107 feed port    -   108 melt    -   110 cooling tube    -   IC indirect cooling zone    -   DC direct cooling zone    -   111 carbon source supply unit    -   112, 112 a, 112 b, 112 c inner tubes    -   113 outer tube    -   114 first indirect cooling zone    -   115 second indirect cooling zone    -   120 a, 120 b virtual planes

1. A carbon-coated metal powder comprising a metal powder and a carboncoating film that covers the metal powder, wherein when 10% value, 50%value, and 90% value in a volume-based cumulative fraction in particlesize distribution measurements by a laser diffraction method are denotedby D10, D50, and D90, respectively, D50 is 300 nm or less, and an SDvalue represented by (D90−D10)/(D50) is 1.5 or less; an oxygen contentin a weight proportion of an oxygen component to the carbon-coated metalpowder of a unit weight is 1500 ppm or less per specific surface area of1 m²/g of the powder; and X represented by Expression (1) is 50 or lesswhen a TMA measurement is performed by raising a temperature from a roomtemperature to 1200° C. at a rate of 5° C./min in a nitrogen-hydrogenreducing atmosphere:X (%)=(X _(200° C.) /X _(MAX))×100  (1) (in Expression (1), X_(MAX) is amaximum shrinkage percentage and X_(200° C.) is a maximum value indifferences, each of which is a difference between a maximum shrinkagepercentage and a minimum shrinkage percentage in a temperature width of200° C.).
 2. The carbon-coated metal powder according to claim 1,wherein when the temperature width of 200° C. giving the X_(200° C.) istaken as not less than T° C. to not more than (T+200)° C., T° C.>400° C.3. The carbon-coated metal powder according to claim 1, wherein X′represented by X′ (%)=(X′_(MAX)/X_(MAX))×100 is 30 or less, whenX′_(MAX) is a maximum shrinkage percentage in a range of from a roomtemperature to 400° C.
 4. The carbon-coated metal powder according toclaim 1, wherein the metal powder includes at least one of nickel andcopper.
 5. A carbon-coated metal powder comprising a nickel-based powderconsisting essentially of nickel only or comprising nickel as a maincomponent, and a carbon coating film that covers the nickel-basedpowder, wherein an oxygen content in a weight proportion of an oxygencomponent to the carbon-coated metal powder of a unit weight is 1500 ppmor less per specific surface area of 1 m²/g of the powder; and in asurface analysis by ESCA, a peak position attributable to 1s of a carbonatom in a position at 11 nm from a particle surface toward a particlecenter is shifted to a low-energy side with respect to the peak positionin a position at 1 nm from the particle surface toward the particlecenter.
 6. The carbon-coated metal powder according to claim 5, whereinin the surface analysis by ESCA, the peak position attributable to 1 sof a carbon atom in the position at 11 nm from the particle surfacetoward the particle center is shifted to a low-energy side by 0.08 eV ormore with respect to the peak position in the position at 1 nm from theparticle surface toward the particle center.
 7. The carbon-coated metalpowder according to claim 5, wherein peaks attributable to nickel oxideand nickel hydroxide are not present.
 8. The carbon-coated metal powderaccording to claim 5, wherein when 10% value, 50% value, and 90% valuein a volume-based cumulative fraction in particle size distributionmeasurements by a laser diffraction method are denoted by D10, D50, andD90, respectively, D50 is 300 nm or less, and an SD value represented by(D90−D10)/(D50) is 1.5 or less; and X represented by Expression (1) is50 or less when a TMA measurement is performed by raising a temperaturefrom a room temperature to 1200° C. at a rate of 5° C./rain in anitrogen-hydrogen reducing atmosphere:X (%)=(X _(200° C.) /X _(MAX))×100  (1) (in Expression (1), X_(MAX) is amaximum shrinkage percentage and X_(200° C.) is a maximum value indifferences, each of which is a difference between a maximum shrinkagepercentage and a minimum shrinkage percentage in a temperature width of200° C.).
 9. The carbon-coated metal powder according to claim 5,wherein the nickel-based powder is a powder consisting essentially ofnickel only or a nickel powder containing copper in an amount of 2 wt. %to 20 wt. %.
 10. A method for manufacturing a carbon-coated metalpowder, comprising: a metal vapor generation step for heating a metallicraw material in a reaction vessel and melting and vaporizing themetallic raw material to generate a metal vapor; a conveying step forconveying the metal vapor by a carrier gas from the reaction vessel to acooling tube; a metal nuclei generation step for cooling the metal vaporinside the cooling tube and generating metal nuclei; and a metal nucleigrowth step for growing the generated metal nuclei, wherein in the metalnuclei generation step, a carbon source is supplied into the coolingtube and endothermically decomposed to cool rapidly the metal vapor andcause the formation of a carbon coating film on the surfaces of themetal nuclei in parallel with the metal nuclei generation.
 11. Themethod for manufacturing a carbon-coated metal powder according to claim10, wherein in the metal nuclei generation step, the carbon source issupplied to a position with a temperature equal to or higher than adecomposition temperature of the carbon source and equal to or less than{(a boiling point of the metallic raw material)+[(the boilingpoint)×10%]}° C.
 12. The method for manufacturing a carbon-coated metalpowder according to claim 10, wherein the decomposition temperature ofthe carbon source is lower than the boiling point of the metallic rawmaterial by 100° C. or more.
 13. The method for manufacturing acarbon-coated metal powder according to claim 10, wherein the metallicraw material includes at least one of nickel and copper.
 14. The methodfor manufacturing a carbon-coated metal powder according to claim 13,wherein the metallic raw material consists essentially of nickel only,consists essentially of copper only, or a nickel-based metallic rawmaterial containing copper at 2 wt. % to 20 wt. %, and the carbon sourceis a methane gas.
 15. The method for manufacturing a carbon-coated metalpowder according to claim 10, wherein the metal nuclei generation stepis performed in an indirect cooling step for indirectly cooling themetal vapor conveyed by the carrier gas from the reaction vessel. 16.The method for manufacturing a carbon-coated metal powder according toclaim 15, wherein the indirect cooling step comprises: a first indirectcooling step; and a second indirect cooling step for performing indirectcooling in a state in which a concentration of the metal vapor in thefirst indirect cooling step has been reduced, and in the second indirectcooling step, the carbon source is endothermically decomposed to coolrapidly the metal vapor and cause the formation of the carbon coatingfilm on the surfaces of the metal nuclei in parallel with the metalnuclei generation.
 17. The method for manufacturing a carbon-coatedmetal powder according to claim 10, comprising after the metal nucleigrowth step: a collection step for collecting a carbon-coated metalpowder obtained by crystallization of the metal nuclei; and a heattreatment step for subjecting the collected carbon-coated metal powderto heat treatment for 1 hour or more to 10 hours or less at 180° C. orhigher to 1000° C. or lower under an inert atmosphere, or for 1 hour ormore to 10 hours or less at 180° C. or higher to 400° C. or lower underan air atmosphere.
 18. The method for manufacturing a carbon-coatedmetal powder according to claim 10, wherein the metallic raw material isheated by plasma in the metal vapor generation step.
 19. A conductivepaste comprising the carbon-coated metal powder according to claim 1, abinder resin, and a solvent.
 20. A multilayer electronic component whichis formed by alternately stacking a plurality of internal conductorpaste layers formed using the conductive paste according to claim 19 anda plurality of unfired ceramic green layers to form a multilayer bodyand firing the multilayer body, thereby forming internal conductorlayers.
 21. The multilayer electronic component according to claim 20,wherein a coverage percentage of the internal conductor layers is higherthan 90%.
 22. A conductive paste comprising the carbon-coated metalpowder according to claim 5, a binder resin, and a solvent.
 23. Amultilayer electronic component which is formed by alternately stackinga plurality of internal conductor paste layers formed using theconductive paste according to claim 22 and a plurality of unfiredceramic green layers to form a multilayer body and firing the multilayerbody, thereby forming internal conductor layers.
 24. The multilayerelectronic component according to claim 23, wherein a coveragepercentage of the internal conductor layers is higher than 90%.